US5049377A - Hair-care composition and methods of treating hair - Google Patents

Hair-care composition and methods of treating hair Download PDF

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Publication number
US5049377A
US5049377A US07/487,335 US48733590A US5049377A US 5049377 A US5049377 A US 5049377A US 48733590 A US48733590 A US 48733590A US 5049377 A US5049377 A US 5049377A
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Prior art keywords
hair
emulsion
silicone polymer
branched
percent
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US07/487,335
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Jo Ann Lamb
Kathy L. Dillon
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Dow Silicones Corp
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Dow Corning Corp
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Assigned to DOW CORNING CORPORATION reassignment DOW CORNING CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: DILLON, KATHY L., LAMB, JO ANN
Priority to CA002036444A priority patent/CA2036444C/en
Priority to DE69101069T priority patent/DE69101069T2/en
Priority to JP03036262A priority patent/JP3029053B2/en
Priority to EP91301702A priority patent/EP0445982B1/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners

Definitions

  • the present invention relates to hair care compositions which contain a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer, preferably polydimethylsiloxane.
  • silicone emulsions can be formulated into conditioners, styling gels, pump sprays, permanent hair waving products, and the like and are especially effective in enhancing the wet and dry combing of hair.
  • Such aminofunctional siloxanes show a stronger affinity for hair surfaces and are not removed as easily as other siloxane polymers.
  • the aminofunctional siloxanes have been shown to have a greater effect in reducing the average combing force.
  • U.S. Pat. No. 4,563,347, issued Jan. 7, 1986, and U.S. Pat. No. 4,749,732, issued June 7, 1988 teach the use of aminoalkyl substituted polydiorganosiloxanes with other components in hair care compositions to improve combing and feel characteristics.
  • Great Britain Patent No. 2,058,103 (published Apr. 8, 1981), discloses hair conditioning compositions containing a cationic polymer and an oil in water emulsion of an aminofunctional polydimethylsiloxane which improves ease of combing.
  • aqueous emulsion composition which can be employed in hair conditioners, which includes a linear polydimethylsiloxane base polymer fluid having a viscosity of up to 100,000 cps.
  • the present invention benefits from a crosslinked polydimethylsiloxane. Crosslinking occurs when polyfunctional compounds having more than two functional groups per molecule are used.
  • a toluene solubility test provides a simple method to distinguish between linear and nonlinear polydimethylsiloxanes because linear siloxanes are soluble in toluene whereas branched and crosslinked siloxanes are not.
  • linear and nonlinear polydimethylsiloxanes exhibit different physical properties.
  • Linear polydimethylsiloxanes are liquids which exhibit viscous flow, even at high molecular weights.
  • Branched or crosslinked polydimethylsiloxanes of comparable molecular weight are elastomers. Since the two classes of siloxane polymers have such significant differences in physical properties, it would not be obvious to substitute a highly branched and crosslinked siloxane for a predominantly linear siloxane in hair treatment compositions.
  • a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer for use in fabric care applications to improve rewettability is described in U.S. Pat. No. 4,908,140, issued Mar. 13, 1990, and assigned to the same assignee as the present application.
  • U.S. Pat. No. 4,908,140 discloses a method of enhancing the rewettability of fabrics treated in a laundering operation by contacting the fabrics with a mixture including a rinse cycle fabric softening conditioning composition and a hydrophobic cationic emulsion of a silicone polymer inorder to improve the water absorbing capabilities of fabrics.
  • hydrophobic cationic emulsion in hair care formulations provides advantages neither taught nor appreciated by U.S. Pat. No. 4,908,140.
  • hair care products were not contemplated by U.S. Pat. No. 4,908,140 and hair treated in accordance with the present invention possesses improved wet and dry combing properties which is unrelated to enhancing water absorbency.
  • the hydrophobic silicone emulsion of the present invention effectively sheets the surface of hair making the hair easier to comb and more desirable to feel. Accordingly, the present invention provides compositions and methods of hair treatment possessing significant advantages over the prior art.
  • This invention is directed to an aqueous hair care formulation in which the improvement comprises incorporating therein a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer, the polymer being an organosiloxane of the formula: ##EQU1## wherein:
  • R is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical and a halogenated monovalent hydrocarbon radical
  • n is an integer having an average value of from one to less than three, the branched and crosslinked silicone polymer being a highly branched and crosslinked polydimethylsiloxane and including less than about forty percent of linear silicone polymer as determined by extraction with toluene.
  • This invention is also related to a method for treating hair by incorporating into hair care formulations an effective amount of the hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer as referred to above.
  • hair as used in the present invention includes treated and untreated human hair, animal hair, and any type of fiber which requires ease of combing, softness and gloss.
  • hydrophobic cationic emulsions of highly branched and crosslinked silicone polymers used in the present invention and methods for their preparation are described in U.S. Pat. No. 4,908,140, which is incorporated herein by reference.
  • hydrophobic cationic emulsions of the present invention that enhance wet and dry combing in hair care formulations are primarily constituted of highly branched and crosslinked polydimethylsiloxanes and substituted derivatives wherein some methyl groups are substituted with organofunctional groups, i.e. amine, carboxyl, amide.
  • the polydimethylsiloxanes used herein are high molecular weight branched and crosslinked polymers having a molecular weight of at least 100,000 and a viscosity above 50,000 centistokes.
  • silicones are formulated into hair care compositions as emulsions.
  • the method of preparation of the emulsions can be any conventional method by which emulsions are typically made.
  • U.S. Pat. No. 2,891,920, issued June 23, 1959, is hereby incorporated by reference as an example of one method of preparing emulsions useable in the present invention.
  • the emulsions prepared using the organofunctional siloxanes of the present invention are oil in water type emulsions. Some water in oil type products are prepared in the initial stages of homogenization during manufacture of the emulsions of this invention but these emulsions soon invert and become oil in water type emulsions.
  • co-surfactants may be used in the preparation of the emulsions of this invention.
  • useful co-surfactants are cationic surfactants and nonionic surfactants.
  • Suitable cationic surfactants include aliphatic amines, aromatic amines with aliphatic substituents, organic quaternary ammonium compounds, polyethylenediamine, polypropanolpolyethanolamines and the like.
  • Preferred cationic surfactants for use in the present invention include ARQUAD® T-27W (N-alkyl trimethyl ammonium chloride), manufactured by Armak, Inc., McCook, Ill. and MIRAPOL® A-15 (polyquaternary ammonium chloride), manufactured by The Miranol Chemical Company, Inc., Dayton, N.J.
  • nonionic surfactants include condensation products of fatty substances with ethylene oxide, condensation products of phenolic compounds having aliphatic side chains with ethylene oxide and the like.
  • Preferred nonionic surfactants for use in the present invention include MAKON® 10 (alkyphenoxy polyoxyethylene ethanol), available from Stepan Chemical Company, Northfield, Ill., and TERGITOL® 15-S-3 (C 11 -C 15 secondary alcohol ethoxylate), available from Union Carbide Corp., Danbury, Conn.
  • the hydrophobic cationic emulsion of this invention is present in hair care formulations in proportions of from 0.05 to 20%, and more preferably from 0.1 to 6%, by weight of the total weight of the composition.
  • Hair care formulations contemplated herein to benefit from addition of the hydrophobic cationic emulsion of this invention include, but are not limited to, conditioners, styling gels and pump sprays, and may be in the form of aqueous or aqueous-alcoholic dispersions and thickened or unthickened creams, gels, aerosol foams or sprays.
  • hair care formulations may contain one or more water soluble quaternised proteins; one or more silicone polymers; conditioning agents; and other adjuvants usually employed in cosmetics, such as sunscreens, perfumes, colorants, preserving agents, sequestering agents, emulsifiers, softeners and foam stabilisers.
  • Natural brown, European virgin hair was used. Three hair tresses per treatment were prepared for each material to be tested. About two grams of hair, root end, were glued to a 2" by 2" plastic tab. The tresses were cut so that the length of hair hanging below the tabs was six inches.
  • the bleaching solution was prepared by mixing seven grams of sodium chloride and 68.0 g of water until the sodium chloride dissolved. To this solution was added 10.0 g of urea, 3.0 g of glycerin and 12.0 g of ammonium hydroxide. The resulting solution was mixed on a 1:1 ratio with 6% hydrogen peroxide.
  • the permanent waving solution included a reducing solution and a neutralizing solution.
  • the reducing solution contained 84.4% distilled water, 7.65% concentrated thioglycolic acid and 7.95% concentrated ammonium hydroxide.
  • the pH of the reducing solution was adjusted to 9.5 with sodium hydroxide.
  • the neutralizing solution contained 92.7% distilled water and 7.3% hydrogen peroxide.
  • the pH of the neutralizing solution was adjusted to 3.6 with phosphoric acid.
  • the bleaching and waving of the tresses was carried out by covering the tresses with the bleaching solution, followed by the reducing solution for twenty minutes each, during which time the tresses were agitated periodically. Each solution was applied only after the previous solution had been removed. The tresses were then rinsed with water before the neutralizing solution was applied. After five minutes, the tresses were again rinsed with water.
  • This shampoo formulation was prepared by heating water to about 40° C. and adding STANDAPOL® A and MONAMID® 1159. This mixture was stirred until a homogenous solution was obtained and KATHON® CG was added.
  • the shampooing of the tresses was carried out by rinsing the tresses for 30 seconds, squeezing out the excess water, applying 0.5 grams of shampoo and lathering for one minute, followed by rinsing with water for one minute.
  • Comparative quantitative combing studies were performed using an Instron Tensile Testing apparatus available from Instron Corporation, Canton, Mass., which had been adapted with a hard rubber comb. This test involved passing a tress through a comb attached to a strain gauge which in turn is connected to a recording device. Measurements were taken of the peak combing force or maximum force to comb through each tress, as well as of the average combing load (ACL) to comb through each tress. The average combing load was determined by integrating the peak combing force and dividing by the length of hair combed in centimeters and is reported as a relative numerical value. The average combing load is an objective measure of the average force required to comb through a tress.
  • This example illustrates the procedure used to prepare the emulsion used in the other examples.
  • This example shows that the incorporation of a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer into a conditioning formulation enhances the combing and feel of both wet and dry hair that has been treated with such formulations.
  • the above conditioning formulation containing the silicone emulsion was prepared by heating water to about 70° C. and adding CERASYNT® Q and POLAWAX®. This mixture was stirred until a homogenous solution was obtained and the silicone emulsion was added.
  • the above comparative organic conditioning formulation was prepared by heating water to about 70° C. and adding CERASYNT® Q, stearalkonium chloride, POLAWAX® and cetyl alcohol. The mixture was stirred until a homogenous solution was obtained.
  • the tresses were shampooed.
  • the tresses were treated with the conditioner containing the silicone emulsion and with the comparative organic conditioner. Three tresses per treatment were used. Where a conditioner was applied, one gram was massaged into the tress for 60 seconds and the tress was rinsed with water at a temperature of about 40° C. Each wet tress was combed on the Instron Tensile Testing apparatus. Three combing strokes were conducted for each tress and averaged to obtain a representative value. Combs were changed for each treatment.
  • the conditioning composition containing the silicone emulsion proved to be superior in terms of ease of combing and desireability of feel than in the cases where the silicone emulsion was not utilized.
  • This example shows that a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer incorporated into a permanent hair waving formulation enhances the combing and feel of both wet and dry hair that has been treated with such a formulation.
  • the silicone emulsion was added to the neutralizing solution of a permanent hair waving formulation and was evaluated against a control which was an identical neutralizing solution without the silicone emulsion. The same reducing solution of the permanent hair waving formulation was used for both treatments.
  • tresses were shampooed and immersed in reducing solution. After 20 minutes, the tresses were rinsed with water having a temperature of about 40° C. The tresses were either immersed in the neutralizing solution containing the silicone emulsion or in the neutralizing solution without the silicone emulsion. Three tresses per treatment were used. After five minutes the tresses were rinsed with water. Each wet tress was combed on the Instron Tensile Testing apparatus. Three combing strokes were conducted for each tress and averaged to obtain a representative value. Combs were changed for each treatment.
  • the permanent hair waving formulation containing the silicone emulsion proved superior in terms of providing ease of combing compared to the waving formulation without the silicone emulsion.
  • the silicone emulsion was added to the neutralizing solution of the permanent hair waving formulation, however, equivalent results can be obtained by adding the silicone emulsion to the reducing part of the formulation.
  • This example shows that a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer incorporated into a styling gel enhances the combing and feel of both wet and dry hair that has been treated with such a formulation.
  • the styling gel was prepared by dissolving QUATERNIUM®-15 into water. CARBOMER® 940 was added to the water. A solution of sodium hydroxide was added followed by PVP/DMAEM® and the remaining ingredients. An equivalent styling gel formulation without the silicone emulsion was also prepared.
  • tresses were shampooed. These tresses were then treated with the styling gel which contained the silicone emulsion or with the styling gel without the silicone emulsion. Three tresses per treatment were used. One-half a gram of the respective styling gels was massaged into each tress for 30 seconds. While still wet, subjective combing and feel tests were conducted on the tresses. The tresses were allowed to dry at room temperature for 18 hours before subjective combing and feel tests were conducted on the dry tresses. The subjective evaluations were conducted by a panel of four people. The evaluators rated the tresses on a scale of 1 for the best to 5. The higher values indicate hair that was harder to comb and hair that felt more coarse when touched. The average of these results are summarized in Table IV.
  • the styling gel containing the silicone emulsion proved to be superior in terms of ease of combing and desireability of feel than the styling gel where the silicone emulsion was not utilized.
  • This example shows a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer incorporated into a hair styling solution known commercially as a "spritz".
  • the hair spritz formulation was prepared by combining the water, GAFQUAT® 734 and PVP/VA® E-735, then adding the silicone emulsion. The mixture was stirred until a homogenous solution was obtained and GLYDANT® was added.
  • This example shows a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer may be incorporated into a conditioner formulation which also contains a sunscreen.
  • the conditioner formulation was prepared by combining the water and UVINUL® MS-40 and adding the silicone emulsion. The mixture was stirred until a homogenous solution was obtained and KATHON® CG was added. Very good combing and feel for both wet and dry hair was obtained after applying this composition to the tresses. In addition, this composition remained stable for at least three months at 40° C.

Abstract

Hair care compositions containing a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer. The silicone polymer is a polydimethylsiloxane and the silicone emulsions can be formulated into conditioners, styling gels, pump sprays and permanent hair waving products. The compositions are effective in enhancing wet and dry combing and feel of hair.

Description

BACKGROUND OF THE INVENTION
The present invention relates to hair care compositions which contain a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer, preferably polydimethylsiloxane. These silicone emulsions can be formulated into conditioners, styling gels, pump sprays, permanent hair waving products, and the like and are especially effective in enhancing the wet and dry combing of hair.
It is well known in the art that the incorporation of polydimethylsiloxanes into hair care formulations enhances the manageability, appearance and feel of treated hair. For example, U.S. Pat. No. 4,243,657, issued Jan. 6, 1981, discloses a hair care composition including polydimethylsiloxanes and diol derivatives or branched aliphatic alcohols. Recently, aminoalkyl substituted polydiorganosiloxanes have become popular in hair care formulations. These aminoalkyl substituted polydiorganosiloxane polymers are typically dimethylsiloxane polymers in which some of the methyl groups attached to the polymer chain are replaced by organic groups of amine functionality. Such aminofunctional siloxanes show a stronger affinity for hair surfaces and are not removed as easily as other siloxane polymers. In addition, the aminofunctional siloxanes have been shown to have a greater effect in reducing the average combing force. U.S. Pat. No. 4,563,347, issued Jan. 7, 1986, and U.S. Pat. No. 4,749,732, issued June 7, 1988, teach the use of aminoalkyl substituted polydiorganosiloxanes with other components in hair care compositions to improve combing and feel characteristics. Great Britain Patent No. 2,058,103, (published Apr. 8, 1981), discloses hair conditioning compositions containing a cationic polymer and an oil in water emulsion of an aminofunctional polydimethylsiloxane which improves ease of combing.
In accordance with the present invention, however, it has been discovered that aminoalkyl groups are not necessary to improve the combing and feel characteristics of hair. Instead, the present inventors have found that it is possible to incorporate a hydrophobic cationic emulsion of a highly branched and crosslinked polydimethylsiloxane, hereinafter referred to as the silicone emulsion, into hair care formulations. The degree of crosslinking distinguishes the emulsion of this invention from other emulsions used in the field of cosmetics. For example, U.S. Pat. No. 4,696,969, issued Sept. 29, 1987, discloses an aqueous emulsion composition which can be employed in hair conditioners, which includes a linear polydimethylsiloxane base polymer fluid having a viscosity of up to 100,000 cps. Unlike the prior art, however, the present invention benefits from a crosslinked polydimethylsiloxane. Crosslinking occurs when polyfunctional compounds having more than two functional groups per molecule are used.
A toluene solubility test provides a simple method to distinguish between linear and nonlinear polydimethylsiloxanes because linear siloxanes are soluble in toluene whereas branched and crosslinked siloxanes are not. In addition to differences in solubility, linear and nonlinear polydimethylsiloxanes exhibit different physical properties. Linear polydimethylsiloxanes are liquids which exhibit viscous flow, even at high molecular weights. Branched or crosslinked polydimethylsiloxanes of comparable molecular weight are elastomers. Since the two classes of siloxane polymers have such significant differences in physical properties, it would not be obvious to substitute a highly branched and crosslinked siloxane for a predominantly linear siloxane in hair treatment compositions.
A hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer for use in fabric care applications to improve rewettability is described in U.S. Pat. No. 4,908,140, issued Mar. 13, 1990, and assigned to the same assignee as the present application. U.S. Pat. No. 4,908,140 discloses a method of enhancing the rewettability of fabrics treated in a laundering operation by contacting the fabrics with a mixture including a rinse cycle fabric softening conditioning composition and a hydrophobic cationic emulsion of a silicone polymer inorder to improve the water absorbing capabilities of fabrics.
However, use of the hydrophobic cationic emulsion in hair care formulations provides advantages neither taught nor appreciated by U.S. Pat. No. 4,908,140. For example, hair care products were not contemplated by U.S. Pat. No. 4,908,140 and hair treated in accordance with the present invention possesses improved wet and dry combing properties which is unrelated to enhancing water absorbency. The hydrophobic silicone emulsion of the present invention effectively sheets the surface of hair making the hair easier to comb and more desirable to feel. Accordingly, the present invention provides compositions and methods of hair treatment possessing significant advantages over the prior art.
SUMMARY OF THE INVENTION
This invention is directed to an aqueous hair care formulation in which the improvement comprises incorporating therein a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer, the polymer being an organosiloxane of the formula: ##EQU1## wherein:
R is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical and a halogenated monovalent hydrocarbon radical; and
n is an integer having an average value of from one to less than three, the branched and crosslinked silicone polymer being a highly branched and crosslinked polydimethylsiloxane and including less than about forty percent of linear silicone polymer as determined by extraction with toluene.
This invention is also related to a method for treating hair by incorporating into hair care formulations an effective amount of the hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer as referred to above.
DETAILED DESCRIPTION OF THE INVENTION
The term "hair" as used in the present invention includes treated and untreated human hair, animal hair, and any type of fiber which requires ease of combing, softness and gloss. The hydrophobic cationic emulsions of highly branched and crosslinked silicone polymers used in the present invention and methods for their preparation are described in U.S. Pat. No. 4,908,140, which is incorporated herein by reference.
The hydrophobic cationic emulsions of the present invention that enhance wet and dry combing in hair care formulations are primarily constituted of highly branched and crosslinked polydimethylsiloxanes and substituted derivatives wherein some methyl groups are substituted with organofunctional groups, i.e. amine, carboxyl, amide. The polydimethylsiloxanes used herein are high molecular weight branched and crosslinked polymers having a molecular weight of at least 100,000 and a viscosity above 50,000 centistokes.
These silicones are formulated into hair care compositions as emulsions. The method of preparation of the emulsions can be any conventional method by which emulsions are typically made. U.S. Pat. No. 2,891,920, issued June 23, 1959, is hereby incorporated by reference as an example of one method of preparing emulsions useable in the present invention. It should be noted that the emulsions prepared using the organofunctional siloxanes of the present invention are oil in water type emulsions. Some water in oil type products are prepared in the initial stages of homogenization during manufacture of the emulsions of this invention but these emulsions soon invert and become oil in water type emulsions. It should be further noted that in some cases where it is desired to optimize the emulsion product, certain co-surfactants may be used in the preparation of the emulsions of this invention. For example, useful co-surfactants are cationic surfactants and nonionic surfactants.
Examples of suitable cationic surfactants include aliphatic amines, aromatic amines with aliphatic substituents, organic quaternary ammonium compounds, polyethylenediamine, polypropanolpolyethanolamines and the like. Preferred cationic surfactants for use in the present invention include ARQUAD® T-27W (N-alkyl trimethyl ammonium chloride), manufactured by Armak, Inc., McCook, Ill. and MIRAPOL® A-15 (polyquaternary ammonium chloride), manufactured by The Miranol Chemical Company, Inc., Dayton, N.J. Examples of suitable nonionic surfactants include condensation products of fatty substances with ethylene oxide, condensation products of phenolic compounds having aliphatic side chains with ethylene oxide and the like. Preferred nonionic surfactants for use in the present invention include MAKON® 10 (alkyphenoxy polyoxyethylene ethanol), available from Stepan Chemical Company, Northfield, Ill., and TERGITOL® 15-S-3 (C11 -C15 secondary alcohol ethoxylate), available from Union Carbide Corp., Danbury, Conn.
The hydrophobic cationic emulsion of this invention is present in hair care formulations in proportions of from 0.05 to 20%, and more preferably from 0.1 to 6%, by weight of the total weight of the composition.
Hair care formulations contemplated herein to benefit from addition of the hydrophobic cationic emulsion of this invention include, but are not limited to, conditioners, styling gels and pump sprays, and may be in the form of aqueous or aqueous-alcoholic dispersions and thickened or unthickened creams, gels, aerosol foams or sprays. In addition, such hair care formulations may contain one or more water soluble quaternised proteins; one or more silicone polymers; conditioning agents; and other adjuvants usually employed in cosmetics, such as sunscreens, perfumes, colorants, preserving agents, sequestering agents, emulsifiers, softeners and foam stabilisers.
The apparatus and testing procedures used herein are as follows:
PREPARATION OF TRESSES
Natural brown, European virgin hair was used. Three hair tresses per treatment were prepared for each material to be tested. About two grams of hair, root end, were glued to a 2" by 2" plastic tab. The tresses were cut so that the length of hair hanging below the tabs was six inches.
BLEACHING/WAVING PROCEDURE
The following solutions and methods of preparation were used in the bleaching and waving of the tresses:
A) Bleaching Solution
The bleaching solution was prepared by mixing seven grams of sodium chloride and 68.0 g of water until the sodium chloride dissolved. To this solution was added 10.0 g of urea, 3.0 g of glycerin and 12.0 g of ammonium hydroxide. The resulting solution was mixed on a 1:1 ratio with 6% hydrogen peroxide.
B) Permanent Waving Solution
The permanent waving solution included a reducing solution and a neutralizing solution. The reducing solution contained 84.4% distilled water, 7.65% concentrated thioglycolic acid and 7.95% concentrated ammonium hydroxide. The pH of the reducing solution was adjusted to 9.5 with sodium hydroxide. The neutralizing solution contained 92.7% distilled water and 7.3% hydrogen peroxide. The pH of the neutralizing solution was adjusted to 3.6 with phosphoric acid.
The bleaching and waving of the tresses was carried out by covering the tresses with the bleaching solution, followed by the reducing solution for twenty minutes each, during which time the tresses were agitated periodically. Each solution was applied only after the previous solution had been removed. The tresses were then rinsed with water before the neutralizing solution was applied. After five minutes, the tresses were again rinsed with water.
SHAMPOO PROCEDURE
Shampoo was prepared according to the following formulation:
______________________________________                                    
Ingredient        Wt. %                                                   
______________________________________                                    
Water             61.95                                                   
STANDAPOL ® A.sup.1                                                   
                  35.0                                                    
MONAMID ® 1159.sup.2                                                  
                  3.0                                                     
KATHON ® CG.sup.3                                                     
                  0.05                                                    
                  100.00                                                  
______________________________________                                    
 .sup.1 STANDAPOL ® A (CTFA Adopted Name: Ammonium Lauryl Sulfate),   
 available from Henkel, Inc., Teaneck, NJ., is the ammonium salt of lauryl
 sulfate where "lauryl" means predominantly a mixture of C12 and C14      
 alcohols, and is used as a surfactant. The "CTFA Adopted Name" is from th
 "CTFA Cosmetic Dictionary", 3rd edition, 1982, published by The Cosmetic,
 Toiletry and Fragrance Association, Inc., Washington, DC.                
 .sup.2 MONAMID ® 1159 (CTFA Adopted Name: Cocamide DEA), available fo
 Mona Industries, Inc., Paterson, NJ., is Ncocoyldiethanolamide, and is   
 used as a cosurfactant.                                                  
 .sup.3 KATHON ® CG (CTFA Adopted Name: Methylchloroisothiazolinine   
 (and) Methylisothiozolonone), available from Rohm and Haas Company, Inc.,
 Philadelphia, PA., is a blend of 5chloro-2-methyl-4-isothiazolin-3-one an
 2methyl-4-isothiazolin-3-one, and is used as a antimicrobial.
This shampoo formulation was prepared by heating water to about 40° C. and adding STANDAPOL® A and MONAMID® 1159. This mixture was stirred until a homogenous solution was obtained and KATHON® CG was added.
The shampooing of the tresses was carried out by rinsing the tresses for 30 seconds, squeezing out the excess water, applying 0.5 grams of shampoo and lathering for one minute, followed by rinsing with water for one minute.
QUANTITATIVE COMBING STUDIES
Comparative quantitative combing studies were performed using an Instron Tensile Testing apparatus available from Instron Corporation, Canton, Mass., which had been adapted with a hard rubber comb. This test involved passing a tress through a comb attached to a strain gauge which in turn is connected to a recording device. Measurements were taken of the peak combing force or maximum force to comb through each tress, as well as of the average combing load (ACL) to comb through each tress. The average combing load was determined by integrating the peak combing force and dividing by the length of hair combed in centimeters and is reported as a relative numerical value. The average combing load is an objective measure of the average force required to comb through a tress.
The invention will be further clarified by a consideration of the following examples. All parts and percentages in the examples are on a weight basis unless otherwise stated.
EXAMPLE 1
This example illustrates the procedure used to prepare the emulsion used in the other examples. A mixture of 52.95 g of water, 8.8 g of ARQUAD® T-27W, 0.65 g of methyltrimethoxysilane and 35.0 g of cyclomethicone, was prepared. This mixture was passed twice through a Manton-Gaulin 15M8BA homogenizer set at 7500 psig. The resulting emulsion was rendered alkaline by the addition of 0.25 g of a 20% sodium hydroxide solution. The emulsion was then heated at 85° C. for nine hours while being stirred. After cooling to 40° C., 0.15 g of concentrated phosphoric acid and 1.7 g MAKON® 10 was added while the emulsion continued to be stirred for one hour. The amount of phosphoric acid added should be such that the pH of the emulsion is between 4.5 to 9.0 and preferably from about 6.5 to about 8.0. The pH of these compositions may be adjusted with any cosmetically acceptable alkalizing or acidifying agent. Upon cooling to room temperature 0.5 g of KATHON® CG was added.
EXAMPLE 2
This example shows that the incorporation of a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer into a conditioning formulation enhances the combing and feel of both wet and dry hair that has been treated with such formulations.
______________________________________                                    
Hair Conditioning Formulation Containing Silicone Emulsion                
Ingredient        Wt. %                                                   
______________________________________                                    
Water             92.3                                                    
Silicone Emulsion 5.7                                                     
CERASYNT ® Q.sup.1                                                    
                  1.0                                                     
POLAWAX ®.sup.2                                                       
                  1.0                                                     
                  100.00                                                  
______________________________________
The above conditioning formulation containing the silicone emulsion was prepared by heating water to about 70° C. and adding CERASYNT® Q and POLAWAX®. This mixture was stirred until a homogenous solution was obtained and the silicone emulsion was added.
An organic conditioning formulation equivalent to the conditioning composition described above but without the silicone emulsion, was prepared according to the following formulation:
______________________________________                                    
Organic Conditioning Formulation                                          
Ingredient         Wt. %                                                  
______________________________________                                    
Water              91.0                                                   
Stearalkonium Chloride                                                    
                   5.0                                                    
CERASYNT ® Q.sup.1                                                    
                   1.0                                                    
POLYWAX ®.sup.2                                                       
                   1.0                                                    
Cetyl Alcohol      2.0                                                    
                   100.00                                                 
______________________________________                                    
 .sup.1 CERASYNT ® Q (CTFA Adopted Name: Glyceryl Stearate SE),       
 available from Van Dyk & Company, Inc., Belleville, NJ., is glyceryl     
 monostearate, and is used as a thickener.                                
 .sup.2 POLAWAX ®, available from Croda, Inc., Newark, NJ., is a      
 nonionic emulsifying wax prepared from higher fatty alcohols and ethylene
 oxide.
The above comparative organic conditioning formulation was prepared by heating water to about 70° C. and adding CERASYNT® Q, stearalkonium chloride, POLAWAX® and cetyl alcohol. The mixture was stirred until a homogenous solution was obtained.
In order to evaluate the conditioning efficacy of the silicone emulsion the tresses were shampooed. The tresses were treated with the conditioner containing the silicone emulsion and with the comparative organic conditioner. Three tresses per treatment were used. Where a conditioner was applied, one gram was massaged into the tress for 60 seconds and the tress was rinsed with water at a temperature of about 40° C. Each wet tress was combed on the Instron Tensile Testing apparatus. Three combing strokes were conducted for each tress and averaged to obtain a representative value. Combs were changed for each treatment. After the average combing load was determined for each wet tress, the tresses were allowed to dry at room temperature for 18 hours before the average combing load was measured on the dry tresses. The test results are summarized in Table I. The higher values indicate hair that was harder to comb.
              TABLE I                                                     
______________________________________                                    
Effect of Silicone Emulsion on the Average Combing Load                   
Treatment         Dry Comb  Wet Comb                                      
______________________________________                                    
Conditioner Containing                                                    
                  9.4       24.9                                          
Silicone Emulsion                                                         
Organic Conditioner                                                       
                  17.8      32.3                                          
(no silicone emulsion)                                                    
Blank (no conditioning                                                    
                  29.5      58.6                                          
additive)                                                                 
______________________________________
Additional evaluations were conducted on the wet and dry tresses and these included subjective combing and feel tests. The subjective evaluations were conducted by a panel of four people. The evaluators rated the tresses on a scale of 1 to 5 with one being the best. The higher values indicate hair that was harder to comb and hair that was more coarse when touched. The average of these results is summarized in Table II.
              TABLE II                                                    
______________________________________                                    
Effect of Conditioner Containing Silicone Emulsion                        
on Subjective Combing and Feel                                            
               Wet      Wet     Dry    Dry                                
Treatment      Comb     Feel    Comb   Feel                               
______________________________________                                    
Conditioner Containing                                                    
               1.33     1.42    1.25   1.33                               
Silicone Emulsion                                                         
Organic Conditioner                                                       
               2.33     2.33    2.31   2.25                               
(no silicone emulsion)                                                    
Blank (no conditioning                                                    
               2.79     2.58    2.50   2.50                               
additive)                                                                 
______________________________________
As Table I and Table II clearly indicate, the conditioning composition containing the silicone emulsion proved to be superior in terms of ease of combing and desireability of feel than in the cases where the silicone emulsion was not utilized.
EXAMPLE 3
This example shows that a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer incorporated into a permanent hair waving formulation enhances the combing and feel of both wet and dry hair that has been treated with such a formulation. In this example, the silicone emulsion was added to the neutralizing solution of a permanent hair waving formulation and was evaluated against a control which was an identical neutralizing solution without the silicone emulsion. The same reducing solution of the permanent hair waving formulation was used for both treatments.
In order to evaluate the effect of the silicone emulsion in a hair waving formulation, tresses were shampooed and immersed in reducing solution. After 20 minutes, the tresses were rinsed with water having a temperature of about 40° C. The tresses were either immersed in the neutralizing solution containing the silicone emulsion or in the neutralizing solution without the silicone emulsion. Three tresses per treatment were used. After five minutes the tresses were rinsed with water. Each wet tress was combed on the Instron Tensile Testing apparatus. Three combing strokes were conducted for each tress and averaged to obtain a representative value. Combs were changed for each treatment. After the average combing load was determined for each wet tress, the tresses were allowed to dry at room temperature for 18 hours before the average combing load was measured on the dry tresses. The test results are summarized in Table III. The higher values, the harder it was to comb the hair.
              TABLE III                                                   
______________________________________                                    
Effect of Silicone Emulsion in Hair Waving Formulation                    
                Average Combing Load                                      
Treatment         Dry Comb  Wet Comb                                      
______________________________________                                    
Neutralizing Solution                                                     
                  19.4      25.0                                          
Containing Silicone                                                       
Emulsion                                                                  
Neutralizing Solution                                                     
                  27.0      70.1                                          
without Silicone Emulsion                                                 
______________________________________
As Table III clearly indicates, the permanent hair waving formulation containing the silicone emulsion proved superior in terms of providing ease of combing compared to the waving formulation without the silicone emulsion. In this example, the silicone emulsion was added to the neutralizing solution of the permanent hair waving formulation, however, equivalent results can be obtained by adding the silicone emulsion to the reducing part of the formulation.
EXAMPLE 4
This example shows that a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer incorporated into a styling gel enhances the combing and feel of both wet and dry hair that has been treated with such a formulation.
______________________________________                                    
Styling Gel Formulation                                                   
Ingredient            Wt. %                                               
______________________________________                                    
Water                 85.0                                                
15.sup.1UM ®      0.1                                                 
CARBOPOL ® 940.sup.2                                                  
                      1.0                                                 
Sodium Hydroxide (20% solution)                                           
                      1.4                                                 
Silicone Emulsion     2.0                                                 
PVP/DMAEM ®.sup.3 10.0                                                
Surfactant.sup.4      0.5                                                 
                      100.00                                              
______________________________________                                    
 .sup.1 QUATERNIUM 15 (CTFA Adopted Name: Quaternium15), available from Do
 Chemical USA, Midland, MI., is cis isomer                                
 1(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantane chloride, and is used as
 a antimicrobial.                                                         
 .sup.2 CARBOPOL ® 940 (CTFA Adopted Name: Carbomer 940), available   
 from B. F. Goodrich Chemical Group, Cleveland, OH., is an acrylic acid   
 polymer crosslinked with a polyfunctional agent, and is used as a        
 thickener.                                                               
 .sup.3 PVP/DMAEM ® (CTFA Adopted Name: PVP/Dimethylaminoethylmeth    
 acrylate Copolymer), available from GAF Corporation, Wayne, NJ., is a    
 copolymer of vinylpyrrolidone and dimethylaminoethylmethacrylate, and is 
 used as a fixative.                                                      
 .sup.4 Surfactant--is any commercially available mixture of silicone     
 glycol copolymer and polydimethylcyclosiloxane.
The styling gel was prepared by dissolving QUATERNIUM®-15 into water. CARBOMER® 940 was added to the water. A solution of sodium hydroxide was added followed by PVP/DMAEM® and the remaining ingredients. An equivalent styling gel formulation without the silicone emulsion was also prepared.
In order to evaluate the effect of the silicone emulsion in a styling gel formulation, tresses were shampooed. These tresses were then treated with the styling gel which contained the silicone emulsion or with the styling gel without the silicone emulsion. Three tresses per treatment were used. One-half a gram of the respective styling gels was massaged into each tress for 30 seconds. While still wet, subjective combing and feel tests were conducted on the tresses. The tresses were allowed to dry at room temperature for 18 hours before subjective combing and feel tests were conducted on the dry tresses. The subjective evaluations were conducted by a panel of four people. The evaluators rated the tresses on a scale of 1 for the best to 5. The higher values indicate hair that was harder to comb and hair that felt more coarse when touched. The average of these results are summarized in Table IV.
              TABLE IV                                                    
______________________________________                                    
Effect of Silicone Emulsion in Styling Gel                                
             Subjective Evaluations                                       
               Wet     Wet      Dry   Dry                                 
Treatment      Comb    Feel     Comb  Feel                                
______________________________________                                    
Styling Gel containing                                                    
               2.17    2.08     1.58  1.83                                
Silicone Emulsion                                                         
Styling Gel without                                                       
               3.33    2.92     3.08  3.17                                
Silicone Emulsion                                                         
______________________________________
As Table IV clearly indicates, the styling gel containing the silicone emulsion proved to be superior in terms of ease of combing and desireability of feel than the styling gel where the silicone emulsion was not utilized.
EXAMPLE 5
This example shows a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer incorporated into a hair styling solution known commercially as a "spritz".
______________________________________                                    
Hair Spritz Formulation                                                   
Ingredient        Wt. %                                                   
______________________________________                                    
Water             95.3                                                    
Silicone Emulsion 1.0                                                     
Conditioner.sup.1 0.5                                                     
GAFQUAT ® 734.sup.2                                                   
                  1.0                                                     
PVP/VA ® E-735.sup.3                                                  
                  2.0                                                     
GLYDANT ®.sup.4                                                       
                  0.2                                                     
                  100.00                                                  
______________________________________                                    
 .sup.1 Conditioner--is any commercially available dimethylsiloxaneglycol 
 copolymer.                                                               
 .sup.2 GAFQUAT ® 734 (CTFA Adopted Name: Polquaternium11), available 
 from GAF Corporation, Wayne, NJ., is a copolymer of vinyl pyrrolidone and
 dimethylaminoethylmethacrylate quaternized with dimethyl sulfate, and is 
 used as a conditioning agent.                                            
 .sup.3 PVP/VA ® E735 (CTFA Adopted Name: PVP/VA Copolymer), available
 from GAF Corporation, Wayne, NJ., is a copolymer of vinylpyrrolidone and 
 vinyl acetate, and is used as a fixative.                                
 .sup.4 GLYDANT ® (CTFA Adopted Name: DMDM Hydantoin), available from 
 Glyco, Inc., Greenwich, CN., is 1(hydroxymethyl)-5,5-dimethyl hydantoin, 
 and is used as a antimicrobial.
The hair spritz formulation was prepared by combining the water, GAFQUAT® 734 and PVP/VA® E-735, then adding the silicone emulsion. The mixture was stirred until a homogenous solution was obtained and GLYDANT® was added.
Very good combing and feel for both wet and dry hair was obtained after applying this composition to the hair. In addition, this composition remained stable for at least three months at 40° C.
EXAMPLE 6
This example shows a hydrophobic cationic emulsion of a highly branched and crosslinked silicone polymer may be incorporated into a conditioner formulation which also contains a sunscreen.
______________________________________                                    
Leave-On Conditioning Formulation with Sunscreen                          
Ingredient        Wt. %                                                   
______________________________________                                    
Water             95.95                                                   
Silicone Emulsion 3.0                                                     
UVINUL ® MS-40.sup.1                                                  
                  1.0                                                     
KATHON ® CG.sup.2                                                     
                  0.05                                                    
                  100.00                                                  
______________________________________                                    
 .sup.1 UVINUL ® MS40 (CTFA Adopted Name: Benzophenone4), available   
 from BASF Wyandotte Corporation, Parsippany, NJ., is                     
 2hydroxy-4-methoxy-benzophen-one-5-sulfonic acid; sulisobenzone, and is  
 used as a UV absorber.                                                   
 .sup.2 KATHON ® CG (CTFA Adopted Name: Methylchloroisothiazolinone   
 (and) Methylisothiozolinone), available from Rohm and Haas Company Inc., 
 Philadelphia, PA., is a blend of 5chloro-2-methyl-4-isothiazolin-3-one an
 2methyl-4-isothiazolin-3-one, and is used as a antimicrobial.
The conditioner formulation was prepared by combining the water and UVINUL® MS-40 and adding the silicone emulsion. The mixture was stirred until a homogenous solution was obtained and KATHON® CG was added. Very good combing and feel for both wet and dry hair was obtained after applying this composition to the tresses. In addition, this composition remained stable for at least three months at 40° C.
It will be apparent from the foregoing that many other variations and modifications may be made in the structures, compounds, compositions and methods described herein without departing substantially from the essential features and concepts of the present invention. Accordingly, it should be clearly understood that the forms of the invention described herein are exemplary only and are not intended as limitations on the scope of the present invention.

Claims (9)

What is claimed is:
1. In a hair treating formulation containing at least one of the materials selected from the group consisting of a conditioning agent, surfactant, neutralizing agent, water soluble quaternised protein, silicone polymer, water, thickener, nonionic emulsifying wax, sunscreen, fixative and antimicrobial, the improvement comprising a conditioning agent which is a hydrophobic cationic aqueous emulsion of a highly branched and crosslinked silicone polymer present in an amount of from 0.05 to 20 percent by weight of the total weight of the composition, the polymer being an organosiloxane of the formula: ##EQU2## wherein: R is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical and a halogenated monovalent hydrocarbon radical; and
n is an integer having an average value of from one to less than three, the branched and crosslinked silicone polymer being a highly branched and crosslinked polydimethylsiloxane and including less than about forty percent of linear silicone polymer as determined by extraction with toluene.
2. The formulation of claim 1 wherein the hair care formulation contains from about one half of one percent to about ten percent by weight of the branched and crosslinked silicone polymer emulsion.
3. The formulation of claim 1 wherein the emulsion of the branched and crosslinked silicone polymer contains about thirty-five percent by weight of polymer.
4. A hair conditioner including the emulsion of claim 1 and at least one conditioning agent.
5. A hair waving composition including the emulsion of claim 1 and at least one neutralizing agent.
6. A hair styling solution including the emulsion of claim 1 and at least one fixative.
7. A hair conditioner including the emulsion of claim 1 and at least one sunscreen.
8. A method for treating hair to enhance the wet and dry combing of hair comprising contacting the hair with a hydrophobic cationic aqueous emulsion of a highly branched and crosslinked silicone polymer present in an amount of from 0.05 to 20 percent by weight of the total weight of the composition, the polymer being an organosiloxane of the formula: ##EQU3## wherein: R is selected from the group consisting of hydrogen, a monovalent hydrocarbon radical and a halogenated monovalent hydrocarbon radical; and
n is an integer having an average value of from one to less than three, the branched and crosslinked silicone polymer being a highly branched and crosslinked polydimethylsiloxane, and including less than about forty percent of linear silicone polymer as determined by extraction with toluene.
9. The method of claim 8 wherein the emulsion of the branched and crosslinked silicone polymer contains about thirty-five percent by weight of polymer.
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US5300285A (en) * 1992-10-13 1994-04-05 Dow Corning Corporation Permanent waving with silicones
US5306434A (en) * 1992-10-20 1994-04-26 Alberto-Culver Company Hair care composition containing dispersed silicone oil
US5310845A (en) * 1992-11-10 1994-05-10 General Electric Company Method of preparing curable siloxane polymers containing integral UV absorbers
US5336419A (en) * 1990-06-06 1994-08-09 The Procter & Gamble Company Silicone gel for ease of ironing and better looking garments after ironing
US5733537A (en) * 1990-07-06 1998-03-31 Dow Corning Corporation Hair fixatives
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US20030172468A1 (en) * 2002-03-13 2003-09-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Gradual permanent coloring of hair using dye intermediates dissolved in alkaline water with a gelling agent
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US6736860B2 (en) 2002-03-12 2004-05-18 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Gradual permanent coloring of hair using dye intermediates dissolved in alkaline water with fatty alcohol
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US5180584A (en) * 1990-01-31 1993-01-19 L'oreal Washing compositions based on insoluble silicones and on a surface-active agent of the polyoxyalkylenated carboxylic ether acid type, and their application in cosmetics and in dermatology
US5152924A (en) * 1990-06-01 1992-10-06 Dow Corning Corporation Rust inhibiting silicone emulsions
US5336419A (en) * 1990-06-06 1994-08-09 The Procter & Gamble Company Silicone gel for ease of ironing and better looking garments after ironing
US5733537A (en) * 1990-07-06 1998-03-31 Dow Corning Corporation Hair fixatives
US6147038A (en) * 1991-05-24 2000-11-14 Dow Corning Corporation Optically clear hair conditioning compositions containing aminofunctional silicone microemulsions
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US6274126B1 (en) * 1998-08-21 2001-08-14 Helene Curtis, Inc. Composition for lightening and highlighting hair
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EP0445982A2 (en) 1991-09-11
DE69101069D1 (en) 1994-03-10
EP0445982B1 (en) 1994-01-26
CA2036444A1 (en) 1991-09-03
EP0445982A3 (en) 1991-09-18
DE69101069T2 (en) 1994-08-11
JP3029053B2 (en) 2000-04-04
JPH0592912A (en) 1993-04-16
CA2036444C (en) 1999-09-21

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